Fragrance keeping material

ABSTRACT

There is provided a fragrance keeping material capable of molding into free shapes in which RB ceramics and/or CRB ceramics of 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm 3 /g in pore volume is used to keep or absorb a fragrance.

FIELD OF THE INVENTION

[0001] This invention relates to a fragrance keeping material and afragrance container which emits the fragrance effectively.

BACKGROUND OF THE INVENTION

[0002] Various kinds of fragrant products have been produced and soldwith recent rise in consumer's sense and requirements for fragrance.

[0003] Such fragrant products are classified into two groups, i.e.,gel-type and liquid-type.

[0004] The gel-type fragrance is further divided into an independentcomposition which comprises polysaccharide as a gelling base materialsuch as agar, carrageenan and gums and a dependent composition whichcomprises water absorbing resins. The independent composition isexcellent in relatively low production cost and visual appearance in useas well as on termination of use due to a decrease in volume thereof andless occurrence of liquid leakage. However, it is a problem of thiscomposition that a vaporizing surface area decreases with gradualreduction of volume thereof due to evaporation so that intensity offragrance is getting low toward termination of use.

[0005] On the other hand, as the dependent composition is fluid andusually kept in a cup-like container, its vaporizing surface area seldomdecreases with the elapse of time, while the level of vaporizing surfacegoes down in the container with a decrease in the composition, whichcauses insufficient aeration and slow-down of vaporization. As a result,intensity of fragrance is inconveniently decreased on the termination ofuse. It is also a problem of this type that the dependent base materialis fluid and would split out of the container when it is overturned.

[0006] A variety of liquid type fragrant products are also manufacturedand on sale widely. Most of them are provided with a wick or thin pipeand a plate to vaporize the agent. Vaporization of this type is keptrelatively constant compared with that of gel type because of nodecrease in or lowering of the vaporizing surface. However, as there isa risk of leaking liquid at all times, it is necessary to carry themcarefully to prevent them from overturning.

SUMMARY OF THE INVENTION

[0007] Accordingly, it is an object of the present invention to providea fragrance keeping material and a fragrance container for keeping aliquid type fragrance without leaking of liquid even if the container isoverturned.

[0008] As a result of concentrated investigation, the inventors havefound that a fragrance keeping material and a fragrance containerwithout leaking of liquid even if the container is overturned can beprovided by adsorbing a fragrance to a molded material or a powder ofporous RB ceramics and/or porous CRB ceramics.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009]FIG. 1a is an illustration of a relatively large pore of CRBceramics;

[0010]FIG. 1b is an illustration of pores of CRB ceramics caused by ricebran;

[0011]FIG. 1c is an illustration of pores of CRB ceramics caused bypolymer chain;

[0012]FIG. 2 is a sketch and a sectional view of ornamental pot made ofa fragrance keeping material of the present invention; and

[0013]FIG. 3 is a sketch of an ornament of artificial flower with afragrance keeping material of the present invention.

PREFERRED EMBODIMENTS OF THE INVENTION

[0014] A porous RB ceramics and/or porous CRB ceramics material used inthe present invention is prepared from a defatted product of rice branas a main raw material and a thermosetting resin.

[0015] As is known, Dr. Kazuo Hokkirigawa, the first inventor of thepresent invention, proposed an idea to obtain a porous carbon materialby the use of rice bran which is by-produced 0.9 million ton/year inJapan or 3.3 million ton/year in the world (see, Kinou Zairyou, Vol. 17,No. 5, pp. 24 to 28, May 1997).

[0016] The above mentioned literature describes a method for preparing acarbon material or so-called RB ceramics by mixing and kneading adefatted product of rice bran and a thermosetting resin, press-moldingthe mixture to form a molded material, drying and then baking the driedmaterial in an atmosphere of inert gas.

[0017] Defatted rice bran used in the present invention is not limitedto a specific species of rice and may either be a product of Japan orforeign countries.

[0018] A thermosetting resin used herein may also be any resin which canbe thermally set and typically includes phenol-, diarylphthalate-,unsaturated polyester-, epoxy-, polyimide- and triazine resins, althougha phenol resin is preferably used.

[0019] A thermoplastic resin such as polyamide may also be used togetherwithout departing from a scope of the present invention.

[0020] A mixing ratio of the defatted rice bran to the thermosettingresin is in the range of 50 to 90:50 to 10 and preferably 70 to 80:30 to20 by weight.

[0021] According to the above mentioned method, difference in ratio ofshrinkage between the press-molded material and the finally moldedmaterial which is baked in an atmosphere of inert gas reached almost25%. Such a difference made it substantially difficult to form aprecisely molded material, but has been finally improved as a result ofdevelopment of CRB ceramics.

[0022] Porous CRB ceramics used in the present invention is an improvedmaterial of RB ceramics obtained from defatted rice bran and athermosetting resin and is prepared by mixing and kneading both of thesematerials. The defatted product of rice bran and the thermosetting resinare mixed and kneaded, primarily baked in an inert gas at 700 to 1,000°C. and ground to form a carbonated powder of about 60 mesh or less. Thepowder is then mixed and kneaded with the thermosetting resin to yield amixture (hereinafter referred to as a CRB precursor), press-molded at apressure of 20 to 30 Mpa and further heat-treated the thus moldedmaterial in an atmosphere of inert gas at 500 to 1,100° C. to form CRBceramics as a molded product.

[0023] CRB ceramics is a porous material having innumerable pores. Thesepores formed in CRB ceramics can be classified into three kinds of typesdepending on a formation process thereof.

[0024] A pore shown in FIG. 1(a) is relatively large one having a porediameter of 5 μm or more, which is formed as a space between CRB fineparticles when they overlap each other. A peak pore value of this typeis about 15 μm.

[0025] What is shown in FIG. 1(b) is a pore having a pore diameter ofless than 5 μm which is formed by fiber structure caused by rice bran. Apeak pore value of this type is about 1.8 μm.

[0026] A pore shown in FIG. 1(c) is a small one having a pore diameterof 0.2 μm or less which is formed as a space between molecular chains ofhigh molecular polymer such as a phenol resin when the polymer iscarbonated at high temperature. A peak pore value of this type is about0.05 μm.

[0027] The thus formed three kinds of pores of CRB ceramics function asa fragrance keeping material corresponding to each pore diameter,respectively.

[0028] The most typical distinction of RB ceramics and CRB ceramics isthat a difference in ratio of shrinkage between molded RB ceramics and afinal product thereof is almost 25%, while that of CRB ceramics is solow as 3% or less, which makes the latter material much useful.

[0029] General properties of RB ceramics and CRB ceramics are as in thefollowing:

[0030] extremely high hardness;

[0031] extremely small heat expansion coefficient;

[0032] porous structure;

[0033] electrical conductivity;

[0034] low specific gravity, light weighted;

[0035] improved abrasion resistance;

[0036] easiness of molding and mold die making;

[0037] capable of being powdered; and

[0038] less negative effect to global environment and more resourceconservation due to rice bran to be used as a starting material.

[0039] Accordingly, when a fragrance container is prepared as a moldedproduct of ornament directly from porous RB ceramics and/or porous CRBceramics as a molded material, it is suitable to use CRB ceramicsbecause of its precise moldability. However, even in the above mentionedcase, RB ceramics should not be excluded from embodiments of the presentinvention, because it is possible to mold RB ceramics by means of alittle bit larger mold die, which is then reduced to a desired sizethrough secondary processing.

[0040] Porosity of porous RB ceramics and/or porous CRB ceramics can becontrolled by changing baking conditions, which is one of characteristicfeatures of these materials.

[0041] It is generally confirmed that such porosity is increased with anincrease in heat-treating temperature.

[0042] When a fragrant containing material is prepared as a moldedproduct directly from porous RB ceramics and/or porous CRB ceramicsaccording to the present invention, the molded product suitably has apore diameter of 10 to 2,000 angstrom and a pore volume of 0.1 to 1.1cm³/g.

[0043] When porous RB ceramics and/or porous CRB ceramics is used in thepresent invention, it is not necessary to consider a difference inshrinkage between RB ceramics and CRB ceramics so that basically eitherof these powdery materials may be used on an equal footing. Particlesize of a RB ceramics or CRB ceramics powder varies depending on thepurpose to be used, although an average particle diameter of 0.1 to1,000 μm is generally used.

[0044] Porosity is an important factor of porous RB ceramics and/orporous CRB ceramics used in the present invention, which is influencedby the primary baking temperature of RB ceramics and by both of theprimary baking temperature and the secondary heat-treating temperatureof CRB ceramics.

[0045] RB ceramics or CRB ceramics of optimum porosity can be yielded byprimary baking or secondary heat treatment thereof at a temperature of800 to 1,000° C.

[0046] When porous RB ceramics and/or porous CRB ceramics is used as apowder, a well-known carbon fine powder may be used together with theceramics powder.

[0047] A ratio of the powder of RB ceramics and/or CRB ceramics to thecarbon powder is suitably 50 to 90:50 to 10 by weight.

[0048] The powder of RB ceramics or CRB ceramics is hard, while itssurface is quite rough, which characteristically increases maintainingproperties thereof as a powdery material.

[0049] Embodiments of the present invention will be summarised as in thefollowing.

[0050] 1. A fragrance keeping material in which a fragrance is adsorbedto a molded product of porous RB ceramics material and/or porous CRBceramics.

[0051] 2. A fragrance keeping material described in the above item 1 inwhich a molded material is a spherical body of 1 to 20 mm in diameter.

[0052] 3. A fragrance keeping material described in the above item 1 inwhich a molded material is a cubic body of 1 to 20 mm in side.

[0053] 4. A fragrance keeping material described in the above item 1 inwhich a molded material is a tablet-like body of 5 to 20 mm in diameter.

[0054] 5. A fragrance keeping material described in the above item 1 inwhich a molded material is a cylindrical body of 1 to 20 mm in diameterand 1 to 20 mm in length.

[0055] 6. A fragrance container in which a molded product described ineither one of the above items 2 to 5 is put is a fragrance containerprovided with an openable and closable lid.

[0056] 7. A fragrance container described in the above item 6 in whichthe fragrance container is an ornamental model.

[0057] 8. A fragrance keeping material described in the above item 1 inwhich a molded product is an ornamental model.

[0058] 9. A fragrance keeping material in which a fragrance is adsorbedto a powder of porous RB ceramics material and/or porous CRB ceramics.

[0059] 10. A fragrance container in which a powder described in theabove item 9 is put is a fragrance container provided with a openableand closeable lid.

[0060] 11. A fragrance container described in the above item 10 in whichthe container is an ornamental model.

[0061] It has been found that a fragrance keeping material of thepresent invention can be molded into free shapes while keepingpredetermined properties due to the use of RB ceramics and CRB ceramics.It has been also found that a powder of RB ceramics and CRB ceramicsexhibits suitable properties as a fragrance keeping material.

[0062] This invention will be further described in the followingexamples.

EXAMPLE 1

[0063] Preparation of CRB ceramics precursor

[0064] A defatted product of rice bran in an amount of 75 kg and aliquid phenol resin (resol) in an amount of 25 kg were mixed and kneadedby heating at 50 to 60° C. to form a plastic and homogeneous mixture.

[0065] The mixture was primarily baked by means of a rotary kiln in anitrogen atmosphere at 900° C. for 60 minutes. The carbonated materialthus baked was screened through a 100-mesh screen to form a carbonatedpowder of 50 to 250 μm in particle diameter.

[0066] The carbonated powder in an amount of 75 kg and a solid phenolresin (resol) in an amount of 25 kg were mixed and kneaded by heating at100 to 150° C. to form a plastic and homogeneous mixture as a plasticCRB ceramics precursor.

[0067] Molding of a fragrance keeping material

[0068] Then, there was made a mold die for molding a spherical body of10.0 cm in diameter, to which the plastic CRB ceramics precursor waspored and press-molded at a pressure of 22 Mpa. The mold die temperaturewas 150° C.

[0069] The thus molded body was taken out of the mold die and subjectedto a heat treatment by heating-up to 500° C. in a nitrogen atmosphere ata heat rising rate of 1° C. per minute and keeping at 500° C. for 60minutes and then at 900° C. for about 60 minutes.

[0070] The molded body was then cooled at a cool down rate of 2 to 3° C.per minute down to 500° C., followed by natural heat dissipation under500° C. to yield a molded spherical body 1 of CRB ceramics.

[0071] Properties of the fragrance keeping material

[0072] The molded spherical body of CRB ceramics showed an average porediameter of 550 angstrom and a pore volume of 0.45 cm³/g, and absorbed afragrance well.

EXAMPLE 2

[0073] Preparation of CRB ceramics precursor

[0074] A defatted product of rice bran in an amount of 75 kg and aliquid phenol resin (resol) in an amount of 25 kg were mixed and kneadedby heating at 50 to 60° C. to form a plastic and homogeneous mixture.

[0075] The mixture was primarily baked by means of a rotary kiln in anitrogen atmosphere at 900° C. for 60 minutes. The carbonated materialthus baked was screened through a 200-mesh screen to form a carbonatedpowder of 50 to 120 μm in particle diameter.

[0076] The carbonated powder in an amount of 75 kg and a solid phenolresin (resol) in an amount of 25 kg were mixed and kneaded by heating at100 to 150° C. to form a plastic and homogeneous mixture as a plasticCRB ceramics precursor.

[0077] Molding of a fragrance keeping material

[0078] Then, there was made a mold die for molding a cubic body of 2 cmin side, to which the plastic CRB ceramics precursor was pored andpress-molded at a pressure of 25 Mpa. The mold die temperature was 150°C.

[0079] The thus molded body was taken out of the mold die and subjectedto a heat treatment by heating-up to 500° C. in a nitrogen atmosphere ata heat rising rate of 1° C. per minute and keeping at 500° C. for 60minutes and then at 1,000° C. for about 150 minutes.

[0080] The molded body was then cooled at a cool down rate of 2 to 3° C.per minute down to 500° C., followed by natural heat dissipation under500° C. to yield a molded cubic body 2 of CRB ceramics.

[0081] Properties of the fragrance keeping material

[0082] The molded product 2 of CRB ceramics 1 showed an average porediameter of 380 angstrom and a pore volume of 0.52 cm³/g, and absorbed afragrance well.

EXAMPLE 3

[0083] Preparation of RB ceramics precursor

[0084] A defatted product of rice bran in an amount of 75 kg and aliquid phenol resin (resol) in an amount of 25 kg were mixed and kneadedby heating at 50 to 60° C. to form a plastic and homogeneous mixture.

[0085] Molding of a fragrance keeping material

[0086] Then, there was made a mold die for molding a spherical body of1.0 cm in diameter similarly as Example 1, to which the plastic RBceramics precursor was pored and press-molded at a pressure of 22 Mpa.The mold die temperature was 170° C.

[0087] The thus molded body was taken out of the mold die and subjectedto a heat treatment by heating-up to 500° C. in a nitrogen atmosphere ata heat rising rate of 1° C. per minute and keeping at 800° C. for 120minutes. The molded body was then cooled at a cool down rate of 2 to 3°C. per minute down to 500° C., followed by natural heat dissipationunder 500° C.

[0088] Properties of the fragrance keeping material

[0089] The molded spherical body of RB ceramics 1 showed an average porediameter of 450 angstrom and a pore volume of 0.50 cm³ /g, and absorbeda fragrance well although it shrank slightly.

EXAMPLE 4

[0090] Preparation of CRB ceramics precursor

[0091] A defatted product of rice bran in an amount of 75 kg and aliquid phenol resin (resol) in an amount of 25 kg were mixed and kneadedby heating at 50 to 60° C. to form a plastic and homogeneous mixture.

[0092] The mixture was primarily baked by means of a rotary kiln in anitrogen atmosphere at 900° C. for 60 minutes. The carbonated materialthus baked was screened through a 300-mesh screen to form a carbonatedpowder of 50 to 80 μm in particle diameter.

[0093] The carbonated powder in an amount of 78 kg and a solid phenolresin (resol) in an amount of 22 kg were mixed and kneaded by heating at100 to 150° C. to form a plastic and homogeneous mixture as a plasticCRB ceramics precursor.

[0094] Molding of a fragrance keeping material

[0095] Then, there was made a mold die for molding an ornamental pot 1having a lid 2 with a perforation 3 as shown in FIG. 2, to which theplastic CRB ceramics precursor was pored and press-molded at a pressureof 22 Mpa. The mold die temperature was 150° C.

[0096] The thus molded body was taken out of the mold die and subjectedto a heat treatment by heating-up to 500° C. in a nitrogen atmosphere ata heat rising rate of 1° C. per minute and keeping at 500° C. for 60minutes and then at 1,000° C. for about 120 minutes.

[0097] The molded body was then cooled at a cool down rate of 2 to 3° C.per minute down to 500° C., followed by natural heat dissipation under500° C. to yield a molded product 1 of CRB ceramics as shown in FIG. 2.

[0098] Properties of the fragrance keeping material

[0099] The molded ornamental pot 1 of CRB ceramics showed an averagepore diameter of 390 angstrom and a pore volume of 0.55 cm³ /g, andabsorbed a fragrance well. The fragrance was successfully keptthroughout the pot itself by directly impregnating the fragrance intothe pot.

EXAMPLE 5

[0100] Preparation of CRB ceramics precursor

[0101] A defatted product of rice bran in an amount of 75 kg and aliquid phenol resin (resol) in an amount of 25 kg were mixed and kneadedby heating at 50 to 60° C. to form a plastic and homogeneous mixture.

[0102] The mixture was primarily baked by means of a rotary kiln in anitrogen atmosphere at 900° C. for 60 minutes. The carbonated materialthus baked was ground by means of a grinder and screened through a200-mesh screen to form a carbonated powder of 50 to 130 μm in particlediameter.

[0103] The carbonated powder in an amount of 75 kg and a solid phenolresin (resol) in an amount of 25 kg were mixed and kneaded by heating at100 to 150° C. to form a plastic and homogeneous mixture.

[0104] Preparation of a powder

[0105] The plastic mixture was then press-molded at a pressure of 20 Mpato form a spherical body of 3 cm in diameter. The mold die temperaturewas 150° C.

[0106] The thus molded body was taken out of the mold die and subjectedto a heat treatment by heating-up to 500° C. in a nitrogen atmosphere ata heat rising rate of 1° C. per minute and keeping at 500° C. for 60minutes and sintering at 950° C. for about 120 minutes.

[0107] The molded body was then cooled at a cool down rate of 2 to 3° C.per minute down to 500° C., followed by natural heat dissipation under500° C.

[0108] The spherical body of 3 cm in diameter was ground by means of agrinder and further finely ground by means of a ball mill to form CRBceramics fine particles of 5 to 10 μm in average particle diameter.

[0109] Properties of the powdery fragrance keeping material

[0110] The RB ceramics fine particles of 7 μm in average particlediameter showed a pore volume of 0.53 cm³/g, and absorbed a fragrancewell.

EXAMPLE 6

[0111] A fragrance was impregnated into fragrance keeping materials 4,which were prepared in Examples 1 to 3, and a proper number of piecesthereof were put in a pot 1 having a lid 2 with a perforation 3, whichwas prepared in Example 4, after taking off the lid 2.

[0112] It is possible to change a fragrance keeping material to new onewhen the fragrance is faded therefrom.

[0113] It is also possible to activate a used fragrance keeping materialwith steam, etc. and further impregnate a fragrance into the materialfor recycling use.

EXAMPLE 7

[0114] As shown in FIG. 3, a base part 5 of artificial flower ornamentwas bored to form a cylindrical space 6, while a fine powdery fragrancekeeping material 7 prepared in Example 5 was impregnated with afragrance and packed in the space.

[0115] The fragrance may be changed depending on the kind of anartificial flower to be decorated. A perforated lid, not shown in FIG.3, may be put on the cylindrical space 6.

[0116] It is possible to change the fragrance keeping material to newone when the fragrance is faded, and to reuse the material for recyclingsimilarly as in the case of Example 6.

What is claimed is:
 1. A fragrance keeping material in which a fragranceis adsorbed to a molded product of porous RB ceramics material and/orporous CRB ceramics.
 2. A fragrance keeping material claimed in claim 1in which a molded material is a spherical body of 1 to 20 mm indiameter.
 3. A fragrance keeping material claimed in claim 1 in which amolded material is a cubic body of 1 to 20 mm in side.
 4. A fragrancekeeping material claimed in claim 1 in which a molded material is atablet-like body of 5 to 20 mm in diameter.
 5. A fragrance keepingmaterial claimed in claim 1 in which a molded material is a cylindricalbody of 1 to 20 mm in diameter and 1 to 20 mm in length.
 6. A fragrancecontainer in which a molded product claimed in either one of claims 2 to5 is put is a fragrance container provided with an openable and closablelid.
 7. A fragrance container claimed in claim 6 in which the fragrancecontainer is an ornamental model.
 8. A fragrance keeping materialclaimed in claim 1 in which a molded product is an ornamental model. 9.A fragrance keeping material in which a fragrance is adsorbed to apowder of porous RB ceramics material and/or porous CRB ceramics.
 10. Afragrance container in which a powder claimed in claim 9 is put is afragrance container provided with an openable and closable lid.
 11. Afragrance container claimed in claim 10 in which the container is anornamental model.